EP0822188B1 - Process for preparing bis (2-hydroxyphenyl-3-benzotriazole) methanes - Google Patents

Process for preparing bis (2-hydroxyphenyl-3-benzotriazole) methanes Download PDF

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Publication number
EP0822188B1
EP0822188B1 EP97305705A EP97305705A EP0822188B1 EP 0822188 B1 EP0822188 B1 EP 0822188B1 EP 97305705 A EP97305705 A EP 97305705A EP 97305705 A EP97305705 A EP 97305705A EP 0822188 B1 EP0822188 B1 EP 0822188B1
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EP
European Patent Office
Prior art keywords
reaction
benzotriazole
product
dissolution
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP97305705A
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German (de)
English (en)
French (fr)
Other versions
EP0822188A1 (en
Inventor
Naoyuki Sugii
Toshiyuki Yamauchi
Eisuke Kanagawa
Hideo Aoki
Kazuyuki Ishihara
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Johoku Chemical Co Ltd
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Johoku Chemical Co Ltd
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/18—Benzotriazoles
    • C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2

Definitions

  • the present invention relates to a novel process for preparing bis(2-hydroxyphenyl-3-benzotriazole) methanes which are useful as ultraviolet absorbers for rubber, plastics and photographic layers.
  • Hydroxyphenylbenzotriazoles themselves are commonly known as ultraviolet absorbers, and methylene bis-type compounds prepared by dimerizing these with methylene bonds are also publicly known as ultraviolet absorbers. Methylene bis-type compounds and processes for their preparation are described in Czechoslovakian Patent No. 141,206, German Patent No. 1,670,951, U.S. Patent No. 3,936,305, Japanese Examined Patent Publication No. 4-58468 (corresponding to European Patent Publication No. 0180993A2) and Japanese Unexamined Patent Publication No. 5-213908.
  • Czechoslovakian Patent No. 141,206 describes a process for dimerizing hydroxyphenylbenzotriazoles with aqueous formalin in a reaction solution
  • German Patent No. 1,670,951 describes a process for dimerizing them with paraformaldehyde in the presence of glacial acetic acid or sulfuric acid
  • Japanese Unexamined Patent Publication No. 5-213908 describes a process for dimerizing with paraformaldehyde or trioxane in concentrated sulfuric acid. With this process the yield of the desired product is higher than that of the former two processes, but it is still insufficient and is in need of improvement.
  • Japanese Examined Patent Publication No. 4-58468 (corresponding to European Patent Publication No. 0180993A2) describes a process involving a 2-step reaction of synthesizing an intermediate (II) from a starting compound (I) with a lower alkylamine and formaldehyde in a solvent, and then dimerizing it to produce the desired product (III), as illustrated by the following reaction formula.
  • X represents a hydrogen atom, halogen atom, alkyl group, allyl group or alkoxy group
  • R represents an alkyl group or arylalkyl group
  • Alk represents a lower alkyl group.
  • the present invention provides a process which allows bis(2-hydroxyphenyl-3-benzotriazole) methanes to be obtained efficiently and at a high yield.
  • the present invention provides a process for preparing a bis(2-hydroxyphenyl-3-benzotriazole) methane which is characterized by reacting a 2-hydroxyphenylbenzotriazole with a formaldehyde and an amino alcohol in an organic solvent in the presence of a basic catalyst.
  • the 2-hydroxyphenylbenzotriazole used as the starting material is a compound which is represented by the following general formula (1): wherein X represents a hydrogen atom, halogen atom, alkyl group, allyl group or alkoxy group and R represents an alkyl group or arylalkyl group.
  • the bis(2-hydroxyphenyl-3-benzotriazole) methane which is the object compound of the process of the invention is a methylene bis-type compound represented by the following general formula (3): wherein X each independently represents a hydrogen atom, halogen atom, alkyl group, allyl group or alkoxy group and each R independently represents an alkyl group or arylalkyl group.
  • the process of the invention is further characterised by using a formaldehyde together with an amino alcohol.
  • Amino alcohol is a general term for amine derivatives with an alcoholic hydroxyl group, and these are also known as alkamines. According to the invention it is particularly suitable to use primary and secondary amino alcohols represented by the following general formula (2): wherein n is an integer of 1 or greater, and a is 1 or 2.
  • Such amino alcohols there may be mentioned monoethanolamine, monopropanolamine, monobutanolamine, diethanolamine, dipropanolamine and dibutanolamine which are readily obtainable in the industry at the current time, but of course there is no limitation to these.
  • formaldehydes for example, formaldehyde, paraformaldehyde, trioxane and tetraoxymethylene.
  • alkali metals there may be used alkali metals, alkaline earth metals and their hydroxides, oxides, hydrides, carbonates, amides and alcoholates.
  • organic solvent may be used as the reaction solvent, and there are no particular restrictions here so long as it is an organic solvent which does not react with the reactants.
  • useful organic solvents there may be mentioned aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and common alcohols or ethers, among which alcohols and ethers are most suitable.
  • the reaction is preferably accomplished by mixing and dissolving the 2-hydroxyphenylbenzotriazole, formaldehyde and amino alcohol in the organic solvent and heating and stirring the mixture at 70-200°C for 1 to 10 hours in the presence of the basic catalyst. After removal of the amino alcohol and solvent under reduced pressure, the bis(2-hydroxyphenyl-3-benzotriazole) methane may be obtained as the desired dimerized product.
  • the formaldehyde may be used in an amount of 0.5-2 moles, and preferably 0.5-1 mole in terms of formaldehyde and the amino alcohol may be used in an amount of 0.1-2 moles, and preferably 0.1-1 mole, with respect to one mole of the 2-hydroxyphenylbenzotriazole.
  • the amount of the formaldehyde is preferably a stoichiometric amount of 0.5 moles or greater in terms of formaldehyde with respect to one mole of the 2-hydroxyphenylbenzotriazole, but if it exceeds one mole there is a tendency for the reaction product to contain many high molecular weight impurities.
  • the amount of the amino alcohol does not need to be the equivalent of 0.5 mole or greater with respect to the formaldehyde since it is not a 2-stage reaction with intermediates, but at lower than 0.1 mole the reaction essentially fails to proceed, while at greater than 1 mole there is a tendency for the yield to gradually decrease.
  • the Mannich reaction is well-known as a reaction for obtaining aminomethylated intermediates from phenols, formaldehydes and alkylamines as disclosed in Japanese Examined Patent Publication No. 4-58468 mentioned above, and such aminomethylated intermediates are called Mannich bases.
  • Mannich bases aminomethylated intermediates from phenols, formaldehydes and alkylamines as disclosed in Japanese Examined Patent Publication No. 4-58468 mentioned above, and such aminomethylated intermediates are called Mannich bases.
  • Mannich bases aminomethylated intermediates
  • directly dimerized products are obtained from 2-hydroxyphenylbenzotriazoles.
  • the processes described above which use alkylamines are 2-stage reactions involving synthesis of Mannich bases followed by dimerization, the intermediates have a high possibility of impurities and high molecular weight byproducts are produced as a result of the long reaction times; however, since the process of the invention does not involve intermediates, the object product may be obtained at a high yield with simple steps and in a short time.
  • Example 1 The procedure of Example 1 was repeated, except that 42 g of 98% monoethanolamine was used instead of di(ethanol)amine.
  • the resulting crude crystals were analyzed by liquid chromatography and found to have a purity of 98% (90% yield).
  • the crude crystals were then recrystallized from the xylene to obtain a purified product of a light yellow-white powder with a melting point of 198°C.
  • the purity of this purified product was determined by liquid chromatography analysis to be 100%.
  • the resulting reaction mixture was cooled to 10°C to obtain crystals, and after filtering the crystals were taken out and dried.
  • the resulting crude product crystals were analyzed by liquid chromatography and found to have a purity of 80% (55% yield).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP97305705A 1996-07-31 1997-07-29 Process for preparing bis (2-hydroxyphenyl-3-benzotriazole) methanes Expired - Lifetime EP0822188B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP20225196 1996-07-31
JP20225196A JP4162274B2 (ja) 1996-07-31 1996-07-31 ビス（２−ヒドロキシフェニル−３−ベンゾトリアゾール）メタン類の製造方法
JP202251/96 1996-07-31

Publications (2)

Publication Number Publication Date
EP0822188A1 EP0822188A1 (en) 1998-02-04
EP0822188B1 true EP0822188B1 (en) 2003-03-12

Family

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Family Applications (1)

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EP97305705A Expired - Lifetime EP0822188B1 (en) 1996-07-31 1997-07-29 Process for preparing bis (2-hydroxyphenyl-3-benzotriazole) methanes

Country Status (4)

Country Link
US (1) US5808086A (ja)
EP (1) EP0822188B1 (ja)
JP (1) JP4162274B2 (ja)
DE (1) DE69719628T2 (ja)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2020629C (en) * 1989-07-21 2000-02-01 Frank Landy Shelf stable fast-cure aqueous coating
JP2963945B2 (ja) * 1997-05-08 1999-10-18 大塚化学株式会社 ２，２’−ビス（６−ベンゾトリアゾリルフェノール）化合物
ES2307755T3 (es) * 2001-10-29 2008-12-01 Chemipro Kasei Kaisha, Limited Transformaciones de cristal que desprenden poco polvo de 2,2'-metilenbis(4-(1,1,3,3-tetrametilbutil)-6-benzotriazolilfenol) y mezclas de las mismas, procedimiento para prepararlas y absorbedor de luz ultravioleta que las usa.
JP4163561B2 (ja) * 2003-06-17 2008-10-08 富士フイルム株式会社 色素化合物
CN103193724B (zh) * 2013-04-08 2016-01-13 南通大学 一种紫外线吸收剂2,2’-亚甲基二[6-(2h-苯并三唑-2-基)-4-叔丁基]苯酚的制备方法
CN103450106B (zh) * 2013-07-30 2015-11-18 浙江常山科润化学有限公司 一种苯并三氮唑紫外线吸收剂uv-360的制备方法
CN106008381A (zh) * 2016-06-01 2016-10-12 杭州欣阳三友精细化工有限公司 一种苯并三唑基-亚烷基双酚化合物的制备方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1670951A1 (de) * 1967-11-21 1971-02-18 Bayer Ag Alkylen-bis-(benztriazolyl-phenole)
JPS516540B2 (ja) * 1973-12-03 1976-02-28
JPS61113667A (ja) * 1984-11-07 1986-05-31 Adeka Argus Chem Co Ltd 耐光性の改善された熱硬化性合成樹脂塗料組成物
JPS61115073A (ja) * 1984-11-09 1986-06-02 Adeka Argus Chem Co Ltd ２，２’−メチレンビス（４−置換−６−ベンゾトリアゾリルフェノ−ル）の製造方法
JPS61118373A (ja) * 1984-11-15 1986-06-05 Adeka Argus Chem Co Ltd ビス（ベンゾトリアゾリルフェノ−ル）化合物
JP2865386B2 (ja) * 1990-06-26 1999-03-08 三洋電機株式会社 非水電解質二次電池
EP0490815B1 (de) * 1990-12-11 1994-09-21 Ciba-Geigy Ag Verfahren zur Herstellung von symmetrischen 2,2'-Methylen-bis-benztriazolylphenolen
US5237071A (en) * 1991-01-22 1993-08-17 Fairmount Chemical Company, Inc. Process for preparing 2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-hydrocarbyl phenols)
DE4118545C2 (de) * 1991-06-06 1994-12-08 Bayer Ag Verfahren zur Herstellung von Derivaten des Bis-[2-hydroxy-phenyl-3(2H)-benztriazol]methans

Also Published As

Publication number Publication date
JPH1045728A (ja) 1998-02-17
EP0822188A1 (en) 1998-02-04
DE69719628T2 (de) 2004-02-05
DE69719628D1 (de) 2003-04-17
US5808086A (en) 1998-09-15
JP4162274B2 (ja) 2008-10-08

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